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CHEMISTRY
ISSN: 2053-2296

Polymorphism in an unexpected caesium complex of 5-hy­droxy­hydurilic acid

aSchool of Natural Sciences (Chemistry), Bedson Building, University of Newcastle, Newcastle upon Tyne NE1 7RU, England
*Correspondence e-mail: w.clegg@ncl.ac.uk

(Received 14 September 2005; accepted 15 September 2005; online 30 September 2005)

Vigorous reaction of barbituric acid with caesium hydroxide in water resulted in an unexpected coupling product, 5-hydroxy­hydurilic acid, complexed to caesium, giving poly[[caesium-μ5-5-hydroxy­hydurilato] hemihydrate], {[Cs(C8H5N4O7)]·0.5H2O}n. This was obtained in two different polymorphic forms, depending on the method of crystal growth. Slow solvent evaporation yielded an ortho­rhombic polymorph, (I)[link], which crystallized in the space group Pnab (non-standard setting of Pbcn), with the uncoordinated water mol­ecule lying on a crystallographic twofold axis. The water mol­ecule is sandwiched into cavities within the structure and is securely held in place by N—H⋯O and O—H⋯O hydrogen bonding. Polymorph (II)[link] is monoclinic, although the unit-cell parameters are similar to those of polymorph (I)[link], and it crystallizes in the space group C2/c, with the uncoordinated water mol­ecule again lying on the twofold axis and secured by hydrogen bonding. The differences between the two polymorphs, both of which have nine-coordinate caesium and a similar first-shell environment of all structural components, are in the overall arrangement of the cations, anions and water mol­ecules, and in the shape of the cavities, revealed by inspecting and comparing crystal-packing diagrams.

Comment

Barbituric acid is a simple mol­ecule which has been much studied in recent times due to its propensity to form polymorphs and, as a result, it has been used as a model compound for developing computational polymorph prediction techniques (Lewis et al., 2004[Lewis, T. C., Tocher, D. A. & Price, S. L. (2004). Cryst. Growth Des. 4, 979-987.]). One of the major obstacles to the success of this research has been the partial flexibility of the mol­ecule, which makes successful polymorph modelling particularly tricky (Lewis et al., 2005[Lewis, T. C., Tocher, D. A. & Price, S. L. (2005). Cryst. Growth Des. 5, 983-993.]). Recently, we demonstrated that this mol­ecular flexibility allows the crystal structure of barbituric acid dihydrate to undergo a phase transition at low temperatures (Nichol & Clegg, 2005[Nichol, G. S. & Clegg, W. (2005). Acta Cryst. B61, 464-472.]).

During the preparation of some alkali metal complexes of barbituric acid, we exposed the reaction with caesium hydroxide to more vigorous conditions than had been used for Li–Rb in order to reduce the solution volume. The result was an unexpected barbiturate coupling product, 5-hydroxy­hydurilic

[Scheme 1]
acid (5-hydr­oxy-5,5′-bibarbituric acid) (see scheme[link]), which coordinated in its anionic form to caesium. Repeating the reaction but with only brief heating of the reaction solution gave a normal barbiturate complex, as for the other alkali metals. We have also observed this same coupling when 1,8-bis­(dimethyl­amino)naphthalene (a proton sponge) was used as the base in a methanolic solution of barbituric acid, so the actual base and solvent used would not seem to be determining factors for the reaction. 5-Hydroxy­hydurilic acid itself is rather unusual; it is not commercially available and the only reported synthesis to date is by electrochemical oxidation of hydurilic acid (and so not actually a barbiturate coupling reaction; Kato et al., 1975[Kato, S., Visinski, B. M. & Dryhurst, G. (1975). J. Electroanal. Chem. 66, 21-43.]).

Crystallization of the reaction product gave two polymorphic forms, (I)[link] and (II)[link]. Crystallization by slow solvent evaporation gave polymorph (I)[link] in the ortho­rhombic space group Pbcn (reported here in the alternative setting Pnab, so that the axes match those in the second polymorph); the space group determination was unambiguous from the systematic absences. The structural unit of polymorph (I)[link] is presented in Fig. 1[link] and is twice the size of the asymmetric unit. It consists of two caesium–5-hydroxy­hydurilate complexes related by a twofold rotation about a non-coordinated but hydrogen-bonded water mol­ecule. The water mol­ecule acts as a donor in two O—H⋯O inter­actions and as an acceptor in two N—H⋯O inter­actions (Table 2[link]) and so is pseudo-tetra­hedral. Additional intra­molecular hydrogen bonding secures the location of the OH group into an S(6) ring (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573. ]). The Cs ion is nine-coordinate (not shown in full in Fig. 1[link]) and the Cs—O bond lengths range from the relatively short 2.981 (2) Å to the rather long 3.531 (2) Å (Table 1[link]). One of the rings of the 5-hydroxy­hydurilate ligand is essentially planar (r.m.s. deviation from a mean plane fitted through the non-H atoms is 0.012 Å), as is usually observed in deprotonated barbituric acid, whilst the second ring contains an sp3-hybridized C atom, which is displaced slightly out of the ring of the remaining non-H atoms (r.m.s. deviation 0.078 Å); the angle between the two mean planes is 85.6 (2)°. The two new bonds formed in the coupling reaction are C4—C5 and C4—O7, which have lengths of 1.502 (4) and 1.439 (3) Å, respectively, indicating that both are single bonds. The hydroxy H atom was easily located in a difference electron-density map, confirming that the C4—O7 bond is single in character. In the planar ring, bonding is delocalized over the O4—C6—C5—C8—O6 segment, with each bond inter­mediate between single and double.

A monoclinic polymorph, (II)[link], was obtained by storing the solution at approximately 278 K for several months. Although the unit-cell parameters of polymorph (II)[link] are similar to those of polymorph (I)[link], this is for a C-centred rather than a primitive unit cell. The structural unit of polymorph (II)[link] is shown in Fig. 2[link]. Like polymorph (I)[link], polymorph (II)[link] crystallizes with one non-coordinating water mol­ecule on a twofold rotation axis, and so the asymmetric unit is one half of the structural unit. Also, as in polymorph (I)[link], the water mol­ecule is secured in place by four hydrogen bonds, as donor for two and as acceptor for the other two, with additional intra­molecular hydrogen bonding securing the position of the hydroxy H atom (Table 4[link]). The Cs ion is again nine-coordinate, but the range of bond lengths is much wider, from 2.983 (4) to 3.690 (4) Å (Table 3[link]), which is distinctly long for a Cs—O bond, but not unknown. The two 5-hydroxy­hydurilate rings are either essentially planar (r.m.s. deviation 0.007 Å for one) or slightly distorted (r.m.s. deviation 0.090 Å for the other), as is seen in polymorph (I)[link], although in polymorph (II)[link], the angle between their two mean planes is slightly smaller, at 78.3 (2)°. Also in common with polymorph (I)[link], the C4—C5 and C4—O7 bond lengths are 1.531 (6) and 1.421 (6) Å, respectively, indicating single-bond character.

If the individual structural units of polymorphs (I)[link] and (II)[link] give little indication that these are two different polymorphic structures, then their respective packing diagrams are more revealing. Fig. 3[link] shows two b-axis projections of polymorphs (I)[link] (top) and (II)[link] (bottom). Setting polymorph (I)[link] in space group Pnab allows a direct comparison to be made between the two, as the cell axes are now approximately equal. Both are three-dimensional structures featuring columns of quadruply bridged Cs centres. These columns are then linked together by further coordination from the second ring of the ligand across to a Cs centre of another column. This linkage creates what appear to be channels within the structure, sandwiched inside which are securely hydrogen-bonded pseudo-tetra­hedral water mol­ecules. Inspection of space-filling models, however, shows that the water mol­ecules lie in individual cavities, between which there are only restricted openings. The differences between the two packing diagrams are in the overall arrangement of the cations, anions and water mol­ecules, and in the shape of the cavities. These are most easily seen by concentrating on the water-filled cavities. In polymorph (I)[link], these apparent channels are arranged such that the overall impression is one of `ripples' within the structure along the c axis. In polymorph (II)[link], there is no such rippling and the apparent channels are stacked ladder-like in a regular rectangular grid.

[Figure 1]
Figure 1
The structural unit of polymorph (I)[link], shown with 50% probability displacement ellipsoids. Dashed lines indicate selected hydrogen bonds.
[Figure 2]
Figure 2
The structural unit of polymorph (II)[link], shown with 50% probability displacement ellipsoids. Dashed lines indicate selected hydrogen bonds.
[Figure 3]
Figure 3
Packing diagrams, projected along the b axes, for polymorphs (I)[link] (top) and (II)[link] (bottom).

Experimental

CsOH·H2O (0.171 g, 1 mmol) and barbituric acid (0.132 g, 1 mmol) were dissolved in distilled water (approximately 30 ml), and the solution was boiled until approximately 10 ml remained. Slow evaporation of a small amount of solvent over a period of one week yielded some very small crystals of polymorph (I)[link]. Storage of the solution at approximately 278 K for around five months yielded small crystal clusters of polymorph (II)[link].

Polymorph (I)[link]

Crystal data
  • [Cs(C8H5N4O7)]·0.5H2O

  • Mr = 411.08

  • Orthorhombic, P n a b

  • a = 13.6671 (8) Å

  • b = 7.0632 (4) Å

  • c = 23.5991 (17) Å

  • V = 2278.1 (2) Å3

  • Z = 8

  • Dx = 2.397 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 19019 reflections

  • θ = 2.5–27.5°

  • μ = 3.30 mm−1

  • T = 150 (2) K

  • Block, colourless

  • 0.30 × 0.10 × 0.10 mm

Data collection
  • Nonius KappaCCD area-detector diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan(SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany.])Tmin = 0.681, Tmax = 0.723

  • 49241 measured reflections

  • 2592 independent reflections

  • 2146 reflections with I > 2σ(I)

  • Rint = 0.065

  • θmax = 27.5°

  • h = −17 → 17

  • k = −9 → 8

  • l = −30 → 30

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.025

  • wR(F2) = 0.047

  • S = 1.05

  • 2592 reflections

  • 204 parameters

  • Only H-atom coordinates refined

  • w = 1/[σ2(Fo2) + (0.0137P)2 + 4.4877P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.68 e Å−3

  • Δρmin = −0.45 e Å−3

Table 1
Selected geometric parameters (Å, °) for polymorph (I)[link]

Cs—O1 3.352 (2)
Cs—O2i 3.2119 (19)
Cs—O3ii 3.1808 (19)
Cs—O4iii 3.1361 (19)
Cs—O4ii 3.469 (2)
Cs—O5iv 2.981 (2)
Cs—O5v 3.320 (2)
Cs—O6 3.531 (2)
Cs—O7vi 3.040 (2)
O4—C6 1.267 (3)
O6—C8 1.253 (3)
O7—C4 1.439 (3)
C1—C4 1.542 (4)
C3—C4 1.530 (4)
C4—C5 1.502 (4)
C5—C6 1.395 (4)
C5—C8 1.399 (4)
C1—C4—C3 113.3 (2) 
C6—C5—C8 120.7 (2)
Symmetry codes: (i) [-x+{\script{1\over 2}}, y, -z]; (ii) [x-{\script{1\over 2}}, -y+1, z]; (iii) [x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (iv) [x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]; (v) x, y-1, z; (vi) [x-{\script{1\over 2}}, -y, z].

Table 2
Hydrogen-bond geometry (Å, °) for polymorph (I)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
O7—H7⋯O4 0.93 (3) 1.65 (3) 2.563 (3) 164 (3)
O8—H8⋯O6 0.72 (3) 2.08 (3) 2.780 (3) 163 (4)
N1—H1N⋯O8v 0.74 (3) 2.16 (3) 2.865 (3) 161 (3)
N2—H2N⋯O3vii 0.73 (3) 2.09 (3) 2.816 (3) 174 (3)
N3—H3N⋯O1viii 0.75 (3) 2.57 (3) 3.151 (3) 136 (3)
N4—H4N⋯O7ii 0.82 (3) 2.29 (3) 3.005 (3) 147 (3)
Symmetry codes: (ii) [x-{\script{1\over 2}}, -y+1, z]; (v) x, y-1, z; (vii) -x+1, -y+1, -z; (viii) [x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}].

Polymorph (II)[link]

Crystal data
  • [Cs(C8H5N4O7)]·0.5H2O

  • Mr = 411.08

  • Monoclinic, C 2/c

  • a = 12.1244 (16) Å

  • b = 8.1353 (11) Å

  • c = 23.267 (3) Å

  • β = 91.654 (2)°

  • V = 2294.0 (5) Å3

  • Z = 8

  • Dx = 2.381 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 7338 reflections

  • θ = 3.0–28.2°

  • μ = 3.28 mm−1

  • T = 150 (2) K

  • Block, colourless

  • 0.30 × 0.18 × 0.15 mm

Data collection
  • Bruker SMART 1K CCD area-detector diffractometer

  • Thin-slice ω scans

  • Absorption correction: multi-scan(SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany.])Tmin = 0.494, Tmax = 0.612

  • 10061 measured reflections

  • 2765 independent reflections

  • 2661 reflections with I > 2σ(I)

  • Rint = 0.031

  • θmax = 28.2°

  • h = −16 → 15

  • k = −10 → 10

  • l = −30 → 30

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.044

  • wR(F2) = 0.082

  • S = 1.42

  • 2765 reflections

  • 204 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • w = 1/[σ2(Fo2) + 28.7093P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.001

  • Δρmax = 1.49 e Å−3

  • Δρmin = −2.50 e Å−3

Table 3
Selected geometric parameters (Å, °) for polymorph (II)[link]

Cs—O2i 2.983 (4)
Cs—O3ii 3.151 (4)
Cs—O1 3.190 (4)
Cs—O4 3.318 (4)
Cs—O4iii 3.009 (3)
Cs—O5iv 3.030 (3)
Cs—O5v 3.181 (4)
Cs—O6ii 3.690 (4)
Cs—O7vi 3.232 (4)
O4—C6 1.260 (6)
O6—C8 1.269 (6)
O7—C4 1.421 (6)
C3—C4 1.534 (7)
C4—C1 1.536 (7)
C4—C5 1.531 (6)
C5—C6 1.403 (7)
C5—C8 1.402 (6)
C3—C4—C1 113.9 (4)
C6—C5—C8 120.0 (4)
Symmetry codes: (i) [-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]; (ii) x, y-1, z; (iii) [-x+{\script{3\over 2}}, -y-{\script{1\over 2}}, -z+2]; (iv) -x+1, -y, -z+2; (v) [x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]; (vi) [x-{\script{1\over 2}}, y-{\script{1\over 2}}, z].

Table 4
Hydrogen-bond geometry (Å, °) for polymorph (II)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
O7—H7⋯O4 0.85 (7) 1.78 (7) 2.567 (5) 154 (6)
O8—H8⋯O6 0.79 (6) 2.03 (6) 2.817 (5) 176 (6)
N2—H2N⋯O8vii 0.86 (3) 2.04 (3) 2.864 (6) 162 (6)
N1—H1N⋯O6i 0.85 (3) 2.16 (3) 3.006 (5) 176 (6)
N3—H3N⋯O3viii 0.83 (3) 2.52 (3) 3.323 (6) 164 (6)
N4—H4N⋯O1ix 0.84 (3) 2.18 (3) 3.005 (6) 168 (6)
Symmetry codes: (i) [-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]; (vii) [x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]; (viii) [-x+{\script{3\over 2}}], [-y+{\script{1\over 2}}], -z+2; (ix) [x-{\script{1\over 2}}, y+{\script{1\over 2}}, z].

All H atoms were located in difference Fourier maps. For polymorph (I)[link], their coordinates were refined freely, with Uiso(H) = 1.2Ueq(O,N); the N—H distance range is 0.74 (3)–0.82 (3) Å, and O—H distances are 0.93 (3) Å for the C—OH H atom and 0.72 (3) Å for the water H atom. For polymorph (II)[link], N—H bond lengths were restrained to 0.85 (3) Å, but O—H distances were not restrained; the O—H distances refined to 0.85 (7) Å for the C—OH H atom and 0.79 (6) Å for the water H atom.

Data collection: COLLECT (Nonius, 1998[Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.]) for polymorph (I)[link]; SMART (Bruker, 2001[Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) for polymorph (II)[link]. Cell refinement: EVALCCD (Duisenberg et al., 2003[Duisenberg, A. J. M., Kroon-Batenburg, L. M. J. & Schreurs, A. M. M. (2003). J. Appl. Cryst. 36, 220-229.]) for polymorph (I)[link]; SAINT (Bruker, 2001[Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) for polymorph (II)[link]. Data reduction: EVALCCD for polymorph (I)[link]; SAINT for polymorph (II)[link]. For both compounds, program(s) used to solve structure: SHELXTL (Sheldrick, 2001[Sheldrick, G. M. (2001). SHELXTL. Version 6.0. Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg & Putz, 2004[Brandenburg, K. & Putz, H. (2004). DIAMOND. Version 3.0. University of Bonn, Germany.]) and MERCURY (Version 1.4; Bruno et al., 2002[Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002). Acta Cryst. B58, 389-397.]); software used to prepare material for publication: SHELXTL and local programs.

Supporting information


Comment top

Barbituric acid is a simple molecule which has been much studied in recent times due to its propensity to form polymorphs and, as a result, it has been used as a model compound for developing computational polymorph prediction techniques (Lewis et al., 2004). One of the major obstacles to the success of this research has been the partial flexibility of the molecule, which makes successful polymorph modelling particularly tricky (Lewis et al., 2005). Recently, we demonstrated that this molecular flexibility allows the crystal structure of barbituric acid dihydrate to undergo a phase transition at low temperatures (Nichol & Clegg, 2005).

During the preparation of some alkali metal complexes of barbituric acid, we exposed the reaction with caesium hydroxide to more vigorous conditions than had been used for Li–Rb in order to reduce the solution volume. The result was an unexpected barbiturate coupling product, 5-hydroxyhydurilic acid (5-hydroxy-5,5'-bibarbituric acid) (see scheme), which coordinated in its anionic form to caesium. Repeating the reaction but with only brief heating of the reaction solution gave a normal barbiturate complex, as for the other alkali metals. We have also observed this same coupling when 1,8-bis(dimethylamino)naphthalene (a proton sponge) was used as the base in a methanolic solution of barbituric acid, so the actual base and solvent used would not seem to be determining factors for the reaction. 5-Hydroxyhydurilic acid itself is rather unusual; it is not commercially available and the only reported synthesis to date is by electrochemical oxidation of hydurilic acid (and so not actually a barbiturate coupling reaction; Kato et al., 1975).

Crystallization of the reaction product gave two polymorphic forms, (I) and (II). Crystallization by slow solvent evaporation gave polymorph (I) in the orthorhombic space group Pbcn (reported here in the alternative setting Pnab, so that the axes match those in the second polymorph); space group determination was unambiguous from the systematic absences. The structural unit of polymorph (I) is presented in Fig. 1 and is twice the size of the asymmetric unit. It consists of two Cs–5-hydroxyhydurilate complexes related by a twofold rotation about a non-coordinated but hydrogen-bonded water molecule. The water molecule acts as a donor in two O—H···O interactions and as an acceptor in two N—H···O interactions (Table 2) and so is pseudo-tetrahedral. Additional intramolecular hydrogen bonding secures the location of the OH group into an R11(6) ring (Bernstein et al., 1995). The Cs ion is nine-coordinate (not shown in full in Fig. 1) and the Cs—O bond lengths range from the relatively short 2.981 (2) Å to the rather long 3.531 (2) Å (Table 1). One of the rings of the 5-hydroxyhydurilate ligand is essentially planar (r.m.s deviation from a mean plane fitted through the non-H atoms is 0.012 Å), as is usually observed in deprotonated barbituric acid, whilst the second ring contains an sp3-hybridized C atom, which is displaced slightly out of the ring of the remaining non-H atoms (r.m.s deviation 0.078 Å); the angle between the two mean planes is 85.6 (2)°. The two new bonds formed in the coupling reaction are C4–C5 and C4–O7, which have lengths of 1.502 (4) and 1.439 (3) Å, respectively, indicating that both are single bonds. The hydroxy H atom was easily located in a difference electron-density map, confirming that the C4—O7 bond is single in character. In the planar ring, bonding is delocalized over the O4—C6—C5—C8—O6 segment, with each bond intermediate between single and double.

A monoclinic polymorph, (II), was obtained by storing the solution at approximately 278 K for several months. Although the unit-cell parameters of polymorph (II) are similar to those of polymorph (I), this is for a C-centred rather than a primitive unit cell. The structural unit of polymorph (II) is shown in Fig. 2. Like polymorph (I), polymorph (II) crystallizes with one non-coordinating water molecule on a twofold rotation axis, and so the asymmetric unit is one half of the structural unit. Also, as in polymorph (I), the water molecule is secured in place by four hydrogen bonds, as donor for two and as acceptor for the other two, with additional intramolecular hydrogen bonding securing the position of the hydroxy H atom (Table 4). The Cs ion is again nine-coordinate, but the range of bond lengths is much wider, from 2.983 (4) to 3.690 (4) Å (Table 3), which is distinctly long for a Cs—O bond, but not unknown. The two 5-hydroxyhydurilate rings are either essentially planar (r.m.s deviation 0.007 Å for one) or slightly distorted (r.m.s deviation 0.090 Å for the other), as is seen in polymorph (I), although in polymorph (II), the angle between their two mean planes is slightly smaller, at 78.3 (2)°. Also in common with polymorph (I), the C4—C5 and C4—O7 bond lengths are 1.531 (6) and 1.421 (6) Å, respectively, indicating single-bond character.

If the individual structural units of polymorphs (I) and (II) give little indication that these are two different polymorphic structures, then their respective packing diagrams are more revealing. Fig. 3 shows two b-axis projections of polymorph (I) (top) and polymorph (II) (bottom). Setting polymorph (I) in space group Pnab allows a direct comparison to be made between the two, as the cell axes are now approximately equal. Both are three-dimensional structures featuring columns of quadruply bridged Cs centres. These columns are then linked together by further coordination from the second ring of the ligand across to a Cs centre of another column. This linkage creates what appear to be channels within the structure, sandwiched inside which are securely hydrogen-bonded pseudo-tetrahedral water molecules. Inspection of space-filling models, however, shows that the water molecules lie in individual cavities, between which there are only restricted openings. The differences between the two packing diagrams are in the overall arrangement of the cations, anions and water molecules, and in the shape of the cavities. These are most easily seen by concentrating on the water-filled cavities. In polymorph (I), these apparent channels are arranged such that the overall impression is one of `ripples' within the structure along the c axis. In polymorph (II), there is no such rippling and the apparent channels are stacked ladder-like in a regular rectangular grid.

Experimental top

CsOH·H2O (0.171 g, 1 mmol) and barbituric acid (0.132 g, 1 mmol) were dissolved in distilled water (approximately 30 ml), and the solution was boiled until approximately 10 ml remained. Slow evaporation of a small amount of solvent over a period of one week yielded some very small crystals of polymorph (I). Storage of the solution at approximately 278 K for around five months yielded small crystal clusters of polymorph (II).

Refinement top

All H atoms were located in difference Fourier maps. For polymorph (I), their coordinates were refined freely, with Uiso(H) = 1.2Ueq(O,N); the N—H distance range is 0.74 (3)–0.82 (3) Å, and O—H distances are 0.93 (3) Å for the C—OH H atom and 0.72 (3) Å for the water H atom. For polymorph (II), N—H bond lengths were restrained to 0.85 (3) Å but O—H distances were not restrained; they refined to 0.85 (7) Å for the C—OH H atom and 0.79 (6) Å for the water H atom.

Computing details top

Data collection: COLLECT (Nonius, 1998) for (I); SMART (Bruker, 2001) for (II). Cell refinement: EVALCCD (Duisenberg et al., 2003) for (I); SAINT (Bruker, 2001) for (II). Data reduction: EVALCCD for (I); SAINT for (II). For both compounds, program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg & Putz, 2004) and Mercury (Version 1.4; Bruno et al., 2002); software used to prepare material for publication: SHELXTL and local programs.

Figures top
[Figure 1] Fig. 1. The structural unit of polymorph (I), with 50% probability displacement ellipsoids. Dashed blue lines indicate selected hydrogen bonds.
[Figure 2] Fig. 2. The structural unit of polymorph (II), with 50% probability displacement ellipsoids. Dashed blue lines indicate selected hydrogen bonds.
[Figure 3] Fig. 3. Packing diagrams, projected along the b axes, for polymorph (I) (top) and polymorph (II) (bottom).
(I) poly[[caesium-µ5-5-hydroxyhydurilato] hemihydrate] top
Crystal data top
[Cs(C8H5N4O7)]·0.5H2OF(000) = 1576
Mr = 411.08Dx = 2.397 Mg m3
Orthorhombic, PnabMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2bc 2nCell parameters from 19019 reflections
a = 13.6671 (8) Åθ = 2.5–27.5°
b = 7.0632 (4) ŵ = 3.30 mm1
c = 23.5991 (17) ÅT = 150 K
V = 2278.1 (2) Å3Block, colourless
Z = 80.30 × 0.10 × 0.10 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
2592 independent reflections
Radiation source: sealed tube2146 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.065
ϕ and ω scansθmax = 27.5°, θmin = 5.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 1717
Tmin = 0.681, Tmax = 0.723k = 98
49241 measured reflectionsl = 3030
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: difference Fourier map
wR(F2) = 0.047Only H-atom coordinates refined
S = 1.05 w = 1/[σ2(Fo2) + (0.0137P)2 + 4.4877P]
where P = (Fo2 + 2Fc2)/3
2592 reflections(Δ/σ)max < 0.001
204 parametersΔρmax = 0.68 e Å3
0 restraintsΔρmin = 0.45 e Å3
Crystal data top
[Cs(C8H5N4O7)]·0.5H2OV = 2278.1 (2) Å3
Mr = 411.08Z = 8
Orthorhombic, PnabMo Kα radiation
a = 13.6671 (8) ŵ = 3.30 mm1
b = 7.0632 (4) ÅT = 150 K
c = 23.5991 (17) Å0.30 × 0.10 × 0.10 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
2592 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2146 reflections with I > 2σ(I)
Tmin = 0.681, Tmax = 0.723Rint = 0.065
49241 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0250 restraints
wR(F2) = 0.047Only H-atom coordinates refined
S = 1.05Δρmax = 0.68 e Å3
2592 reflectionsΔρmin = 0.45 e Å3
204 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cs0.039034 (13)0.16344 (2)0.162529 (7)0.01976 (6)
O10.27214 (15)0.0371 (3)0.13963 (9)0.0246 (5)
O20.40390 (15)0.0331 (3)0.03639 (8)0.0228 (5)
O30.45309 (15)0.5577 (3)0.06914 (8)0.0225 (5)
O40.42089 (15)0.4654 (3)0.23028 (8)0.0234 (5)
O50.13690 (15)0.8022 (3)0.23249 (8)0.0236 (5)
O60.19927 (14)0.4358 (3)0.07812 (8)0.0194 (4)
O70.46294 (14)0.2385 (3)0.14908 (8)0.0187 (4)
H70.454 (2)0.306 (5)0.1827 (15)0.022*
O80.25000.7135 (4)0.00000.0225 (7)
H80.226 (3)0.647 (5)0.0188 (15)0.027*
N10.34024 (18)0.0346 (3)0.05267 (10)0.0175 (5)
H1N0.320 (2)0.060 (5)0.0459 (14)0.021*
N20.42811 (18)0.2934 (3)0.01760 (10)0.0169 (5)
H2N0.456 (2)0.336 (5)0.0055 (14)0.020*
N30.27789 (18)0.6291 (4)0.22977 (11)0.0194 (5)
H3N0.290 (2)0.664 (5)0.2590 (15)0.023*
N40.16987 (18)0.6193 (3)0.15560 (10)0.0169 (5)
H4N0.121 (2)0.658 (4)0.1398 (14)0.020*
C10.3226 (2)0.1149 (4)0.10423 (11)0.0149 (6)
C20.3914 (2)0.1144 (4)0.00827 (11)0.0165 (6)
C30.42043 (19)0.3970 (4)0.06569 (11)0.0139 (5)
C40.37791 (19)0.2995 (4)0.11806 (11)0.0141 (6)
C50.31484 (19)0.4330 (4)0.15152 (11)0.0136 (5)
C60.34233 (19)0.5046 (4)0.20429 (11)0.0167 (6)
C70.1912 (2)0.6910 (4)0.20785 (12)0.0175 (6)
C80.22785 (19)0.4917 (4)0.12570 (11)0.0153 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cs0.02383 (10)0.01822 (9)0.01723 (9)0.00228 (8)0.00056 (7)0.00095 (8)
O10.0319 (12)0.0226 (11)0.0193 (10)0.0079 (9)0.0064 (9)0.0016 (9)
O20.0303 (12)0.0246 (11)0.0134 (10)0.0041 (9)0.0021 (8)0.0054 (9)
O30.0316 (12)0.0190 (10)0.0169 (10)0.0105 (9)0.0076 (9)0.0016 (8)
O40.0197 (10)0.0317 (12)0.0190 (10)0.0031 (9)0.0066 (8)0.0039 (9)
O50.0223 (11)0.0243 (12)0.0242 (11)0.0024 (9)0.0049 (8)0.0047 (9)
O60.0210 (11)0.0215 (10)0.0158 (10)0.0015 (8)0.0061 (8)0.0008 (8)
O70.0171 (10)0.0239 (10)0.0151 (10)0.0048 (9)0.0030 (8)0.0026 (8)
O80.0307 (18)0.0145 (15)0.0222 (17)0.0000.0016 (13)0.000
N10.0231 (13)0.0122 (12)0.0170 (12)0.0060 (10)0.0028 (10)0.0023 (10)
N20.0208 (12)0.0195 (13)0.0103 (11)0.0066 (10)0.0048 (9)0.0020 (10)
N30.0200 (13)0.0227 (13)0.0153 (12)0.0015 (10)0.0036 (10)0.0056 (10)
N40.0138 (12)0.0190 (12)0.0180 (12)0.0022 (9)0.0033 (10)0.0006 (10)
C10.0149 (14)0.0140 (13)0.0159 (13)0.0005 (11)0.0004 (11)0.0024 (10)
C20.0154 (13)0.0190 (14)0.0150 (13)0.0011 (11)0.0029 (11)0.0002 (11)
C30.0116 (12)0.0167 (13)0.0134 (13)0.0007 (11)0.0005 (10)0.0012 (11)
C40.0122 (13)0.0173 (14)0.0129 (13)0.0004 (11)0.0000 (10)0.0008 (10)
C50.0114 (12)0.0168 (13)0.0125 (13)0.0026 (10)0.0025 (10)0.0017 (10)
C60.0160 (14)0.0169 (13)0.0171 (13)0.0032 (12)0.0008 (11)0.0008 (12)
C70.0171 (14)0.0175 (14)0.0180 (14)0.0041 (12)0.0036 (11)0.0009 (11)
C80.0160 (14)0.0145 (13)0.0156 (13)0.0043 (11)0.0024 (10)0.0025 (12)
Geometric parameters (Å, º) top
Cs—O13.352 (2)O7—Csxi3.040 (2)
Cs—O2i3.2119 (19)O7—H70.93 (3)
Cs—O3ii3.1808 (19)O7—C41.439 (3)
Cs—O4iii3.1361 (19)O8—H80.72 (3)
Cs—O4ii3.469 (2)N1—H1N0.74 (3)
Cs—O5iv2.981 (2)N1—C11.364 (4)
Cs—O5v3.320 (2)N1—C21.380 (4)
Cs—O63.531 (2)N2—H2N0.73 (3)
Cs—O7vi3.040 (2)N2—C21.379 (4)
Cs—N43.687 (2)N2—C31.354 (4)
Cs—C6ii3.701 (3)N3—H3N0.75 (3)
Cs—C83.576 (3)N3—C61.382 (4)
O1—C11.214 (3)N3—C71.365 (4)
O2—Csi3.2119 (19)N4—H4N0.82 (3)
O2—C21.212 (3)N4—C71.365 (4)
O3—Csvii3.1808 (19)N4—C81.392 (3)
O3—C31.222 (3)C1—Csxi3.809 (3)
O4—Csviii3.1361 (19)C1—C41.542 (4)
O4—Csvii3.469 (2)C3—C41.530 (4)
O4—C61.267 (3)C4—C51.502 (4)
O5—Csix2.981 (2)C5—C61.395 (4)
O5—Csx3.320 (2)C5—C81.399 (4)
O5—C71.227 (3)C6—Csvii3.701 (3)
O6—C81.253 (3)C7—Csix3.704 (3)
O1—Cs—O2i62.84 (5)Csi—O2—C2134.80 (18)
O1—Cs—O3ii113.83 (5)Csvii—O3—C3139.11 (18)
O1—Cs—O4iii122.83 (5)Csviii—O4—Csvii110.57 (6)
O1—Cs—O4ii135.87 (5)Csviii—O4—C6152.89 (17)
O1—Cs—O5iv78.18 (5)Csvii—O4—C690.36 (16)
O1—Cs—O5v59.52 (5)Csix—O5—Csx119.02 (6)
O1—Cs—O657.63 (5)Csix—O5—C7117.05 (17)
O1—Cs—O7vi93.42 (5)Csx—O5—C7119.99 (17)
O1—Cs—N476.37 (5)Cs—O6—C881.91 (15)
O1—Cs—C6ii154.41 (6)Csxi—O7—H7115 (2)
O1—Cs—C856.47 (6)Csxi—O7—C4127.48 (15)
O2i—Cs—O3ii67.97 (5)H7—O7—C4100.2 (19)
O2i—Cs—O4iii142.13 (5)H1N—N1—C1120 (3)
O2i—Cs—O4ii139.17 (5)H1N—N1—C2113 (3)
O2i—Cs—O5iv139.06 (5)C1—N1—C2126.7 (2)
O2i—Cs—O5v98.21 (5)H2N—N2—C2117 (3)
O2i—Cs—O658.84 (5)H2N—N2—C3116 (3)
O2i—Cs—O7vi73.67 (5)C2—N2—C3127.0 (2)
O2i—Cs—N495.24 (5)H3N—N3—C6118 (3)
O2i—Cs—C6ii127.21 (5)H3N—N3—C7115 (3)
O2i—Cs—C877.60 (6)C6—N3—C7126.3 (2)
O3ii—Cs—O4iii123.26 (5)Cs—N4—H4N85 (2)
O3ii—Cs—O4ii71.31 (5)Cs—N4—C7112.82 (16)
O3ii—Cs—O5iv122.54 (5)Cs—N4—C874.52 (14)
O3ii—Cs—O5v165.74 (5)H4N—N4—C7118 (2)
O3ii—Cs—O660.04 (5)H4N—N4—C8117 (2)
O3ii—Cs—O7vi112.32 (5)C7—N4—C8125.2 (2)
O3ii—Cs—N466.89 (5)Csxi—C1—O187.64 (16)
O3ii—Cs—C6ii61.57 (5)Csxi—C1—N188.28 (16)
O3ii—Cs—C872.34 (6)Csxi—C1—C488.79 (14)
O4iii—Cs—O4ii66.92 (3)O1—C1—N1121.7 (2)
O4iii—Cs—O5iv69.88 (5)O1—C1—C4121.0 (2)
O4iii—Cs—O5v65.37 (5)N1—C1—C4117.0 (2)
O4ii—Cs—O5iv65.00 (5)O2—C2—N1122.6 (2)
O4ii—Cs—O5v122.61 (5)O2—C2—N2121.4 (3)
O4iii—Cs—O6158.85 (5)N1—C2—N2116.0 (2)
O4ii—Cs—O697.87 (5)O3—C3—N2121.9 (3)
O4iii—Cs—O7vi68.72 (5)O3—C3—C4120.2 (2)
O4ii—Cs—O7vi126.48 (5)N2—C3—C4117.6 (2)
O4iii—Cs—N4122.61 (5)O7—C4—C1104.5 (2)
O4ii—Cs—N465.56 (5)O7—C4—C3103.8 (2)
O4iii—Cs—C6ii66.11 (6)O7—C4—C5112.6 (2)
O4ii—Cs—C6ii20.02 (5)C1—C4—C3113.3 (2)
O4iii—Cs—C8139.09 (6)C1—C4—C5111.1 (2)
O4ii—Cs—C887.59 (5)C3—C4—C5111.1 (2)
O5iv—Cs—O5v70.04 (3)C4—C5—C6122.8 (2)
O5iv—Cs—O690.65 (5)C4—C5—C8116.4 (2)
O5v—Cs—O6116.71 (5)C6—C5—C8120.7 (2)
O5iv—Cs—O7vi123.18 (5)Csvii—C6—O469.61 (15)
O5v—Cs—O7vi58.14 (5)Csvii—C6—N3100.12 (17)
O5iv—Cs—N462.10 (5)Csvii—C6—C5100.81 (16)
O5v—Cs—N4119.85 (5)O4—C6—N3117.9 (2)
O5iv—Cs—C6ii84.05 (6)O4—C6—C5125.5 (3)
O5v—Cs—C6ii130.32 (5)N3—C6—C5116.6 (2)
O5iv—Cs—C870.43 (6)Csix—C7—O545.79 (14)
O5v—Cs—C8109.17 (6)Csix—C7—N399.07 (17)
O6—Cs—O7vi131.47 (5)Csix—C7—N4127.34 (17)
O6—Cs—N436.70 (5)O5—C7—N3123.4 (3)
O6—Cs—C6ii104.81 (5)O5—C7—N4122.4 (3)
O6—Cs—C820.29 (5)N3—C7—N4114.1 (2)
O7vi—Cs—N4167.66 (5)Cs—C8—O677.80 (15)
O7vi—Cs—C6ii111.78 (6)Cs—C8—N483.44 (15)
O7vi—Cs—C8145.78 (6)Cs—C8—C5108.39 (16)
N4—Cs—C6ii79.09 (6)O6—C8—N4118.7 (2)
N4—Cs—C822.04 (6)O6—C8—C5124.2 (2)
C6ii—Cs—C8100.26 (6)N4—C8—C5117.1 (2)
Cs—O1—C1121.99 (17)
O2i—Cs—O1—C157.6 (2)O7—C4—C5—C8176.8 (2)
O3ii—Cs—O1—C111.1 (2)C1—C4—C5—C6123.4 (3)
O4iii—Cs—O1—C1165.9 (2)C1—C4—C5—C859.9 (3)
O4ii—Cs—O1—C176.2 (2)C3—C4—C5—C6109.4 (3)
O5iv—Cs—O1—C1109.5 (2)C3—C4—C5—C867.3 (3)
O5v—Cs—O1—C1176.9 (2)Csviii—O4—C6—Csvii141.6 (4)
O6—Cs—O1—C111.07 (19)Csviii—O4—C6—N350.7 (5)
O7vi—Cs—O1—C1127.3 (2)Csvii—O4—C6—N390.9 (2)
N4—Cs—O1—C145.7 (2)Csviii—O4—C6—C5129.5 (3)
C6ii—Cs—O1—C162.5 (3)Csvii—O4—C6—C588.9 (3)
C8—Cs—O1—C135.3 (2)C7—N3—C6—Csvii106.3 (3)
O1—Cs—O6—C880.13 (16)C7—N3—C6—O4178.5 (3)
O2i—Cs—O6—C8155.75 (17)C7—N3—C6—C51.3 (4)
O3ii—Cs—O6—C8123.30 (16)C4—C5—C6—Csvii71.6 (3)
O4iii—Cs—O6—C817.9 (2)C4—C5—C6—O41.0 (4)
O4ii—Cs—O6—C860.25 (16)C4—C5—C6—N3178.8 (2)
O5iv—Cs—O6—C84.60 (16)C8—C5—C6—Csvii105.0 (2)
O5v—Cs—O6—C872.49 (16)C8—C5—C6—O4177.5 (3)
O7vi—Cs—O6—C8142.36 (15)C8—C5—C6—N32.2 (4)
N4—Cs—O6—C832.43 (15)Csx—O5—C7—Csix157.5 (2)
C6ii—Cs—O6—C879.42 (16)Csix—O5—C7—N367.8 (3)
O1—Cs—N4—C798.52 (18)Csx—O5—C7—N3134.8 (2)
O1—Cs—N4—C823.66 (14)Csix—O5—C7—N4112.6 (2)
O2i—Cs—N4—C7158.92 (18)Csx—O5—C7—N444.9 (3)
O2i—Cs—N4—C836.74 (15)C6—N3—C7—Csix137.9 (2)
O3ii—Cs—N4—C7137.74 (19)C6—N3—C7—O5179.9 (3)
O3ii—Cs—N4—C8100.09 (15)C6—N3—C7—N40.2 (4)
O4iii—Cs—N4—C722.0 (2)Cs—N4—C7—Csix36.4 (2)
O4ii—Cs—N4—C758.62 (18)Cs—N4—C7—O592.7 (3)
O4iii—Cs—N4—C8144.13 (14)Cs—N4—C7—N387.6 (2)
O4ii—Cs—N4—C8179.20 (16)C8—N4—C7—Csix123.1 (2)
O5iv—Cs—N4—C714.84 (17)C8—N4—C7—O5179.4 (3)
O5v—Cs—N4—C756.32 (19)C8—N4—C7—N30.9 (4)
O5iv—Cs—N4—C8107.33 (16)Cs—O6—C8—N475.4 (2)
O5v—Cs—N4—C865.85 (16)Cs—O6—C8—C5104.1 (3)
O6—Cs—N4—C7151.9 (2)Cs—N4—C8—O672.2 (2)
O6—Cs—N4—C829.71 (13)Cs—N4—C8—C5107.3 (2)
O7vi—Cs—N4—C7133.3 (2)C7—N4—C8—Cs107.3 (2)
O7vi—Cs—N4—C811.2 (3)C7—N4—C8—O6179.5 (2)
C6ii—Cs—N4—C774.16 (18)C7—N4—C8—C50.0 (4)
C6ii—Cs—N4—C8163.67 (16)C4—C5—C8—Cs89.6 (2)
C8—Cs—N4—C7122.2 (3)C4—C5—C8—O62.1 (4)
Cs—O1—C1—Csxi171.96 (11)C4—C5—C8—N4178.4 (2)
Cs—O1—C1—N1101.5 (3)C6—C5—C8—Cs93.6 (2)
Cs—O1—C1—C484.8 (3)C6—C5—C8—O6178.9 (3)
C2—N1—C1—Csxi97.9 (3)C6—C5—C8—N41.6 (4)
C2—N1—C1—O1176.0 (3)O1—Cs—C8—O686.57 (16)
C2—N1—C1—C410.1 (4)O1—Cs—C8—N4152.10 (17)
Csi—O2—C2—N1160.72 (18)O1—Cs—C8—C535.73 (16)
Csi—O2—C2—N219.5 (4)O2i—Cs—C8—O621.09 (15)
C3—N2—C2—O2178.8 (3)O2i—Cs—C8—N4142.42 (15)
C3—N2—C2—N11.0 (4)O2i—Cs—C8—C5101.21 (18)
C1—N1—C2—O2180.0 (3)O3ii—Cs—C8—O649.46 (15)
C1—N1—C2—N20.2 (4)O3ii—Cs—C8—N471.87 (15)
Csvii—O3—C3—N2151.2 (2)O3ii—Cs—C8—C5171.76 (19)
Csvii—O3—C3—C422.9 (4)O4iii—Cs—C8—O6170.23 (13)
C2—N2—C3—O3177.6 (3)O4ii—Cs—C8—O6120.60 (15)
C2—N2—C3—C48.1 (4)O4iii—Cs—C8—N448.90 (18)
Csxi—O7—C4—C111.7 (3)O4ii—Cs—C8—N40.73 (15)
Csxi—O7—C4—C3107.34 (19)O4iii—Cs—C8—C567.5 (2)
Csxi—O7—C4—C5132.43 (18)O4ii—Cs—C8—C5117.10 (17)
O3—C3—C4—O778.2 (3)O5iv—Cs—C8—O6175.12 (17)
O3—C3—C4—C1169.0 (2)O5v—Cs—C8—O6115.59 (15)
O3—C3—C4—C543.0 (3)O5iv—Cs—C8—N463.55 (15)
N2—C3—C4—O796.1 (3)O5v—Cs—C8—N4123.09 (14)
N2—C3—C4—C116.7 (3)O5iv—Cs—C8—C552.82 (17)
N2—C3—C4—C5142.7 (2)O5v—Cs—C8—C56.71 (19)
Csxi—C1—C4—O77.38 (16)O6—Cs—C8—N4121.3 (2)
Csxi—C1—C4—C3105.00 (19)O6—Cs—C8—C5122.3 (3)
Csxi—C1—C4—C5129.05 (18)O7vi—Cs—C8—O654.5 (2)
O1—C1—C4—O779.1 (3)O7vi—Cs—C8—N4175.78 (13)
O1—C1—C4—C3168.5 (2)O7vi—Cs—C8—C567.8 (2)
O1—C1—C4—C542.5 (3)N4—Cs—C8—O6121.3 (2)
N1—C1—C4—O794.8 (3)N4—Cs—C8—C5116.4 (2)
N1—C1—C4—C317.5 (3)C6ii—Cs—C8—O6105.03 (15)
N1—C1—C4—C5143.5 (2)C6ii—Cs—C8—N416.30 (16)
O7—C4—C5—C66.5 (4)C6ii—Cs—C8—C5132.67 (17)
Symmetry codes: (i) x+1/2, y, z; (ii) x1/2, y+1, z; (iii) x1/2, y+1/2, z+1/2; (iv) x, y1/2, z+1/2; (v) x, y1, z; (vi) x1/2, y, z; (vii) x+1/2, y+1, z; (viii) x+1/2, y+1/2, z+1/2; (ix) x, y+1/2, z+1/2; (x) x, y+1, z; (xi) x+1/2, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O7—H7···O40.93 (3)1.65 (3)2.563 (3)164 (3)
O8—H8···O60.72 (3)2.08 (3)2.780 (3)163 (4)
N1—H1N···O8v0.74 (3)2.16 (3)2.865 (3)161 (3)
N2—H2N···O3xii0.73 (3)2.09 (3)2.816 (3)174 (3)
N3—H3N···O1ix0.75 (3)2.57 (3)3.151 (3)136 (3)
N4—H4N···O7ii0.82 (3)2.29 (3)3.005 (3)147 (3)
Symmetry codes: (ii) x1/2, y+1, z; (v) x, y1, z; (ix) x, y+1/2, z+1/2; (xii) x+1, y+1, z.
(II) poly[[caesium-µ5-5-hydroxyhydurilato] hemihydrate] top
Crystal data top
[Cs(C8H5N4O7)]·0.5H2OF(000) = 1576
Mr = 411.08Dx = 2.381 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 7338 reflections
a = 12.1244 (16) Åθ = 3.0–28.2°
b = 8.1353 (11) ŵ = 3.28 mm1
c = 23.267 (3) ÅT = 150 K
β = 91.654 (2)°Block, colourless
V = 2294.0 (5) Å30.30 × 0.18 × 0.15 mm
Z = 8
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
2765 independent reflections
Radiation source: sealed tube2661 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
thin–slice ω scansθmax = 28.2°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 1615
Tmin = 0.494, Tmax = 0.612k = 1010
10061 measured reflectionsl = 3030
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: difference Fourier map
wR(F2) = 0.082H atoms treated by a mixture of independent and constrained refinement
S = 1.42 w = 1/[σ2(Fo2) + 28.7093P]
where P = (Fo2 + 2Fc2)/3
2765 reflections(Δ/σ)max = 0.001
204 parametersΔρmax = 1.49 e Å3
4 restraintsΔρmin = 2.50 e Å3
Crystal data top
[Cs(C8H5N4O7)]·0.5H2OV = 2294.0 (5) Å3
Mr = 411.08Z = 8
Monoclinic, C2/cMo Kα radiation
a = 12.1244 (16) ŵ = 3.28 mm1
b = 8.1353 (11) ÅT = 150 K
c = 23.267 (3) Å0.30 × 0.18 × 0.15 mm
β = 91.654 (2)°
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
2765 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2661 reflections with I > 2σ(I)
Tmin = 0.494, Tmax = 0.612Rint = 0.031
10061 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0444 restraints
wR(F2) = 0.082H atoms treated by a mixture of independent and constrained refinement
S = 1.42 w = 1/[σ2(Fo2) + 28.7093P]
where P = (Fo2 + 2Fc2)/3
2765 reflectionsΔρmax = 1.49 e Å3
204 parametersΔρmin = 2.50 e Å3
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cs0.69061 (2)0.30528 (4)0.917618 (12)0.01215 (9)
O10.8404 (3)0.0961 (5)0.83409 (16)0.0196 (8)
O20.8860 (3)0.2939 (6)0.70033 (16)0.0266 (9)
O30.8878 (3)0.4636 (5)0.88516 (17)0.0211 (8)
O40.7836 (3)0.0344 (4)0.98136 (15)0.0159 (7)
O50.4318 (3)0.2246 (5)0.97422 (15)0.0167 (8)
O60.6450 (3)0.3386 (5)0.82163 (15)0.0165 (8)
O70.9269 (3)0.1364 (5)0.91048 (15)0.0154 (7)
H70.896 (5)0.085 (8)0.938 (3)0.019*
O80.50000.1546 (6)0.75000.0146 (10)
H80.539 (5)0.210 (8)0.769 (3)0.018*
N10.8440 (4)0.1048 (5)0.76762 (18)0.0139 (8)
H1N0.843 (5)0.031 (6)0.742 (2)0.017*
N20.8803 (4)0.3796 (5)0.79307 (18)0.0136 (8)
H2N0.903 (5)0.473 (5)0.781 (2)0.016*
N30.6087 (3)0.1294 (5)0.97575 (17)0.0116 (8)
H3N0.603 (5)0.089 (7)1.0081 (15)0.014*
N40.5413 (3)0.2792 (5)0.89897 (18)0.0127 (8)
H4N0.488 (4)0.328 (7)0.883 (2)0.015*
C10.8411 (4)0.0502 (6)0.8229 (2)0.0112 (9)
C20.8711 (4)0.2631 (6)0.7504 (2)0.0127 (9)
C30.8710 (4)0.3536 (6)0.8503 (2)0.0127 (9)
C40.8408 (4)0.1805 (6)0.8707 (2)0.0114 (9)
C50.7280 (4)0.1863 (6)0.8985 (2)0.0102 (8)
C60.7122 (4)0.1135 (6)0.9523 (2)0.0119 (9)
C70.5211 (4)0.2129 (6)0.9513 (2)0.0118 (9)
C80.6408 (4)0.2701 (5)0.8705 (2)0.0102 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cs0.01245 (14)0.01435 (15)0.00964 (14)0.00019 (12)0.00023 (9)0.00157 (12)
O20.031 (2)0.035 (2)0.0134 (18)0.0100 (19)0.0027 (16)0.0075 (18)
O30.024 (2)0.0163 (19)0.023 (2)0.0057 (15)0.0065 (16)0.0072 (16)
O10.0238 (19)0.0135 (18)0.0218 (19)0.0005 (15)0.0029 (15)0.0001 (15)
O40.0141 (17)0.0186 (18)0.0151 (17)0.0039 (14)0.0005 (14)0.0064 (14)
O50.0131 (17)0.020 (2)0.0169 (17)0.0025 (14)0.0044 (14)0.0008 (15)
O60.0131 (16)0.022 (2)0.0146 (17)0.0003 (14)0.0024 (13)0.0061 (14)
O70.0087 (16)0.026 (2)0.0114 (16)0.0046 (14)0.0030 (13)0.0031 (15)
O80.020 (3)0.008 (2)0.016 (3)0.0000.002 (2)0.000
N20.016 (2)0.010 (2)0.015 (2)0.0021 (16)0.0030 (16)0.0041 (16)
N10.018 (2)0.014 (2)0.0103 (19)0.0032 (17)0.0018 (16)0.0031 (16)
N30.0127 (19)0.0124 (19)0.0099 (19)0.0019 (15)0.0025 (15)0.0037 (16)
N40.0097 (19)0.012 (2)0.016 (2)0.0031 (15)0.0001 (15)0.0037 (16)
C20.006 (2)0.018 (2)0.014 (2)0.0028 (17)0.0002 (17)0.0030 (19)
C30.006 (2)0.015 (2)0.017 (2)0.0002 (17)0.0027 (17)0.0027 (19)
C40.011 (2)0.013 (2)0.010 (2)0.0011 (18)0.0001 (17)0.0014 (18)
C10.007 (2)0.013 (2)0.013 (2)0.0016 (17)0.0007 (17)0.0007 (18)
C50.008 (2)0.010 (2)0.013 (2)0.0001 (17)0.0034 (16)0.0014 (18)
C60.013 (2)0.009 (2)0.014 (2)0.0004 (17)0.0008 (18)0.0007 (18)
C70.014 (2)0.011 (2)0.011 (2)0.0000 (18)0.0004 (17)0.0017 (18)
C80.014 (2)0.006 (2)0.011 (2)0.0024 (16)0.0001 (17)0.0004 (17)
Geometric parameters (Å, º) top
Cs—O2i2.983 (4)O7—Csx3.232 (3)
Cs—O3ii3.151 (4)O7—H70.85 (7)
Cs—O13.190 (4)O7—C41.421 (6)
Cs—O43.318 (4)O8—H80.79 (6)
Cs—O4iii3.009 (3)N2—H2N0.86 (3)
Cs—O5iv3.030 (3)N2—C21.375 (7)
Cs—O5v3.181 (4)N2—C31.356 (6)
Cs—O6ii3.690 (4)N1—H1N0.85 (3)
Cs—O7vi3.232 (4)N1—C21.391 (6)
Cs—C3ii3.890 (5)N1—C11.363 (6)
Cs—C63.509 (5)N3—H3N0.83 (3)
Cs—C8ii3.669 (5)N3—C61.389 (6)
O2—Csvii2.983 (4)N3—C71.371 (6)
O2—C21.209 (6)N4—H4N0.84 (3)
O3—Csviii3.151 (4)N4—C71.360 (6)
O3—C31.221 (6)N4—C81.395 (6)
O1—C11.218 (6)C3—Csviii3.890 (5)
O4—Csiii3.009 (3)C3—C41.534 (7)
O4—C61.260 (6)C4—C11.536 (7)
O5—Csiv3.030 (3)C4—C51.531 (6)
O5—Csix3.181 (4)C5—C61.403 (7)
O5—C71.225 (6)C5—C81.402 (6)
O6—Csviii3.690 (4)C8—Csviii3.669 (4)
O6—C81.269 (6)
O2i—Cs—O3ii99.15 (11)C3ii—Cs—C8ii45.40 (10)
O2i—Cs—O157.50 (11)C6—Cs—C8ii173.37 (11)
O2i—Cs—O4iii155.34 (12)Csvii—O2—C2141.1 (4)
O2i—Cs—O4106.18 (11)Csviii—O3—C3118.9 (3)
O2i—Cs—O5iv123.96 (10)Cs—O1—C1131.2 (3)
O2i—Cs—O5v128.18 (11)Cs—O4—Csiii81.93 (9)
O2i—Cs—O6ii67.56 (10)Cs—O4—C688.0 (3)
O2i—Cs—O7vi73.21 (11)Csiii—O4—C6142.2 (3)
O2i—Cs—C3ii89.20 (11)Csiv—O5—Csix83.92 (8)
O2i—Cs—C688.17 (12)Csiv—O5—C7147.0 (3)
O2i—Cs—C8ii86.30 (11)Csix—O5—C7128.9 (3)
O3ii—Cs—O173.91 (10)Csviii—O6—C879.2 (3)
O3ii—Cs—O4iii75.84 (10)Csx—O7—H7119 (4)
O3ii—Cs—O4110.70 (9)Csx—O7—C4134.7 (3)
O3ii—Cs—O5iv136.19 (10)H7—O7—C4106 (4)
O3ii—Cs—O5v56.63 (9)H2N—N2—C2114 (4)
O3ii—Cs—O6ii59.20 (9)H2N—N2—C3119 (4)
O3ii—Cs—O7vi131.05 (10)C2—N2—C3126.5 (4)
O3ii—Cs—C3ii15.96 (10)H1N—N1—C2117 (4)
O3ii—Cs—C6125.60 (10)H1N—N1—C1116 (4)
O3ii—Cs—C8ii59.08 (10)C2—N1—C1126.0 (4)
O1—Cs—O468.65 (9)H3N—N3—C6115 (4)
O1—Cs—O4iii139.32 (10)H3N—N3—C7119 (4)
O1—Cs—O5iv133.75 (10)C6—N3—C7125.5 (4)
O1—Cs—O5v71.27 (10)H4N—N4—C7116 (4)
O1—Cs—O6ii97.36 (9)H4N—N4—C8119 (4)
O1—Cs—O7vi128.81 (10)C7—N4—C8125.7 (4)
O1—Cs—C3ii78.38 (10)O2—C2—N2122.8 (5)
O1—Cs—C665.29 (10)O2—C2—N1120.8 (5)
O1—Cs—C8ii114.33 (10)N2—C2—N1116.4 (4)
O4—Cs—O4iii98.07 (9)Csviii—C3—O345.2 (3)
O4iii—Cs—O5iv61.81 (10)Csviii—C3—N2110.4 (3)
O4iii—Cs—O5v69.55 (9)Csviii—C3—C4112.9 (3)
O4—Cs—O5iv67.46 (9)O3—C3—N2121.4 (5)
O4—Cs—O5v56.97 (9)O3—C3—C4120.3 (4)
O4iii—Cs—O6ii89.81 (9)N2—C3—C4118.3 (4)
O4—Cs—O6ii165.33 (8)O7—C4—C3104.8 (4)
O4iii—Cs—O7vi91.69 (9)O7—C4—C1106.3 (4)
O4—Cs—O7vi117.91 (9)O7—C4—C5112.4 (4)
O4iii—Cs—C3ii79.98 (10)C3—C4—C1113.9 (4)
O4—Cs—C3ii125.89 (9)C3—C4—C5109.1 (4)
O4—Cs—C621.03 (10)C1—C4—C5110.3 (4)
O4iii—Cs—C6114.61 (11)O1—C1—N1121.4 (5)
O4iii—Cs—C8ii70.29 (10)O1—C1—C4121.3 (4)
O4—Cs—C8ii165.59 (9)N1—C1—C4117.3 (4)
O5iv—Cs—O5v96.08 (9)C4—C5—C6120.7 (4)
O5iv—Cs—O6ii127.18 (9)C4—C5—C8119.3 (4)
O5v—Cs—O6ii115.49 (8)C6—C5—C8120.0 (4)
O5iv—Cs—O7vi64.34 (9)Cs—C6—O470.9 (3)
O5v—Cs—O7vi158.22 (9)Cs—C6—N396.8 (3)
O5iv—Cs—C3ii141.58 (10)Cs—C6—C5102.5 (3)
O5v—Cs—C3ii72.58 (10)O4—C6—N3116.8 (4)
O5iv—Cs—C668.53 (11)O4—C6—C5125.9 (4)
O5v—Cs—C676.64 (10)N3—C6—C5117.3 (4)
O5iv—Cs—C8ii111.82 (10)O5—C7—N3122.8 (4)
O5v—Cs—C8ii109.70 (10)O5—C7—N4122.9 (4)
O6ii—Cs—O7vi73.91 (9)N3—C7—N4114.3 (4)
O6ii—Cs—C3ii43.31 (9)Csviii—C8—O681.0 (3)
O6ii—Cs—C6155.54 (10)Csviii—C8—N486.9 (3)
O6ii—Cs—C8ii19.85 (9)Csviii—C8—C5101.7 (3)
O7vi—Cs—C3ii116.20 (10)O6—C8—N4117.4 (4)
O7vi—Cs—C6102.80 (10)O6—C8—C5125.4 (4)
O7vi—Cs—C8ii72.08 (10)N4—C8—C5117.2 (4)
C3ii—Cs—C6138.23 (11)
O2i—Cs—O1—C180.7 (4)C3—C4—C5—C6131.3 (5)
O3ii—Cs—O1—C1167.0 (5)C3—C4—C5—C846.6 (6)
O4—Cs—O1—C146.4 (4)C1—C4—C5—C6102.9 (5)
O4iii—Cs—O1—C1123.5 (4)C1—C4—C5—C879.2 (5)
O5iv—Cs—O1—C127.2 (5)Csiii—O4—C6—Cs74.1 (4)
O5v—Cs—O1—C1107.4 (4)Cs—O4—C6—N388.1 (4)
O6ii—Cs—O1—C1138.1 (4)Csiii—O4—C6—N313.9 (8)
O7vi—Cs—O1—C162.9 (5)Cs—O4—C6—C591.8 (5)
C3ii—Cs—O1—C1177.3 (5)Csiii—O4—C6—C5166.0 (4)
C6—Cs—O1—C123.9 (4)C7—N3—C6—Cs109.1 (4)
C8ii—Cs—O1—C1148.9 (4)C7—N3—C6—O4178.8 (5)
O2i—Cs—O4—Csiii175.49 (9)C7—N3—C6—C51.3 (7)
O2i—Cs—O4—C632.0 (3)C4—C5—C6—Cs78.0 (4)
O3ii—Cs—O4—Csiii77.84 (10)C4—C5—C6—O42.6 (8)
O3ii—Cs—O4—C6138.7 (3)C4—C5—C6—N3177.5 (4)
O1—Cs—O4—Csiii140.08 (11)C8—C5—C6—Cs104.2 (4)
O1—Cs—O4—C676.5 (3)C8—C5—C6—O4179.5 (5)
O4iii—Cs—O4—Csiii0.0C8—C5—C6—N30.4 (7)
O4iii—Cs—O4—C6143.4 (3)O2i—Cs—C6—O4149.3 (3)
O5iv—Cs—O4—Csiii54.87 (9)O2i—Cs—C6—N394.6 (3)
O5v—Cs—O4—Csiii59.12 (9)O2i—Cs—C6—C525.4 (3)
O5iv—Cs—O4—C688.6 (3)O3ii—Cs—C6—O449.4 (3)
O5v—Cs—O4—C6157.4 (3)O3ii—Cs—C6—N3165.4 (2)
O6ii—Cs—O4—Csiii121.9 (3)O3ii—Cs—C6—C574.6 (3)
O6ii—Cs—O4—C694.6 (4)O1—Cs—C6—O494.6 (3)
O7vi—Cs—O4—Csiii96.25 (10)O1—Cs—C6—N3149.4 (3)
O7vi—Cs—O4—C647.2 (3)O1—Cs—C6—C529.4 (3)
C3ii—Cs—O4—Csiii83.43 (12)O4iii—Cs—C6—O440.4 (3)
C3ii—Cs—O4—C6133.1 (3)O4—Cs—C6—N3116.0 (4)
C6—Cs—O4—Csiii143.4 (3)O4iii—Cs—C6—N375.6 (3)
C8ii—Cs—O4—Csiii35.2 (4)O4—Cs—C6—C5124.0 (4)
C8ii—Cs—O4—C6178.7 (4)O4iii—Cs—C6—C5164.4 (3)
Csvii—O2—C2—N2147.7 (4)O5iv—Cs—C6—O482.8 (3)
Csvii—O2—C2—N132.6 (8)O5v—Cs—C6—O419.3 (3)
C3—N2—C2—O2176.2 (5)O5iv—Cs—C6—N333.2 (3)
C3—N2—C2—N13.5 (7)O5v—Cs—C6—N3135.4 (3)
C1—N1—C2—O2169.8 (5)O5iv—Cs—C6—C5153.2 (3)
C1—N1—C2—N29.9 (7)O5v—Cs—C6—C5104.6 (3)
Csviii—O3—C3—N288.2 (5)O6ii—Cs—C6—O4142.4 (2)
Csviii—O3—C3—C493.1 (5)O6ii—Cs—C6—N3101.5 (3)
C2—N2—C3—Csviii135.8 (4)O6ii—Cs—C6—C518.5 (4)
C2—N2—C3—O3175.1 (5)O7vi—Cs—C6—O4138.3 (3)
C2—N2—C3—C43.7 (7)O7vi—Cs—C6—N322.3 (3)
Csx—O7—C4—C337.8 (5)O7vi—Cs—C6—C597.7 (3)
Csx—O7—C4—C183.1 (5)C3ii—Cs—C6—O462.6 (3)
Csx—O7—C4—C5156.1 (3)C3ii—Cs—C6—N3178.7 (2)
Csviii—C3—C4—O7104.9 (3)C3ii—Cs—C6—C561.3 (3)
Csviii—C3—C4—C1139.4 (3)Csiv—O5—C7—N349.0 (9)
Csviii—C3—C4—C515.7 (4)Csix—O5—C7—N3138.0 (4)
O3—C3—C4—O754.6 (6)Csiv—O5—C7—N4132.2 (5)
O3—C3—C4—C1170.4 (4)Csix—O5—C7—N440.9 (7)
O3—C3—C4—C565.9 (6)C8—N4—C7—O5179.9 (5)
N2—C3—C4—O7124.1 (4)C8—N4—C7—N30.9 (7)
N2—C3—C4—C18.3 (6)C6—N3—C7—O5179.2 (5)
N2—C3—C4—C5115.4 (5)C6—N3—C7—N41.9 (7)
Cs—O1—C1—N1132.8 (4)Csviii—O6—C8—N481.7 (4)
Cs—O1—C1—C448.2 (6)Csviii—O6—C8—C598.1 (5)
C2—N1—C1—O1163.7 (5)C7—N4—C8—Csviii102.2 (5)
C2—N1—C1—C415.3 (7)C7—N4—C8—O6179.7 (4)
O7—C4—C1—O150.5 (6)C7—N4—C8—C50.6 (7)
O7—C4—C1—N1128.5 (4)C4—C5—C8—Csviii84.2 (4)
C3—C4—C1—O1165.4 (4)C4—C5—C8—O63.0 (7)
C3—C4—C1—N113.6 (6)C4—C5—C8—N4176.7 (4)
C5—C4—C1—O171.6 (6)C6—C5—C8—Csviii93.7 (4)
C5—C4—C1—N1109.4 (5)C6—C5—C8—O6179.1 (5)
O7—C4—C5—C615.5 (6)C6—C5—C8—N41.2 (7)
O7—C4—C5—C8162.4 (4)
Symmetry codes: (i) x+3/2, y1/2, z+3/2; (ii) x, y1, z; (iii) x+3/2, y1/2, z+2; (iv) x+1, y, z+2; (v) x+1/2, y1/2, z; (vi) x1/2, y1/2, z; (vii) x+3/2, y+1/2, z+3/2; (viii) x, y+1, z; (ix) x1/2, y+1/2, z; (x) x+1/2, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O7—H7···O40.85 (7)1.78 (7)2.567 (5)154 (6)
O8—H8···O60.79 (6)2.03 (6)2.817 (5)176 (6)
N2—H2N···O8x0.86 (3)2.04 (3)2.864 (6)162 (6)
N1—H1N···O6i0.85 (3)2.16 (3)3.006 (5)176 (6)
N3—H3N···O3xi0.83 (3)2.52 (3)3.323 (6)164 (6)
N4—H4N···O1ix0.84 (3)2.18 (3)3.005 (6)168 (6)
Symmetry codes: (i) x+3/2, y1/2, z+3/2; (ix) x1/2, y+1/2, z; (x) x+1/2, y+1/2, z; (xi) x+3/2, y+1/2, z+2.

Experimental details

(I)(II)
Crystal data
Chemical formula[Cs(C8H5N4O7)]·0.5H2O[Cs(C8H5N4O7)]·0.5H2O
Mr411.08411.08
Crystal system, space groupOrthorhombic, PnabMonoclinic, C2/c
Temperature (K)150150
a, b, c (Å)13.6671 (8), 7.0632 (4), 23.5991 (17)12.1244 (16), 8.1353 (11), 23.267 (3)
α, β, γ (°)90, 90, 9090, 91.654 (2), 90
V3)2278.1 (2)2294.0 (5)
Z88
Radiation typeMo KαMo Kα
µ (mm1)3.303.28
Crystal size (mm)0.30 × 0.10 × 0.100.30 × 0.18 × 0.15
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Bruker SMART 1K CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.681, 0.7230.494, 0.612
No. of measured, independent and
observed [I > 2σ(I)] reflections
49241, 2592, 2146 10061, 2765, 2661
Rint0.0650.031
(sin θ/λ)max1)0.6500.665
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.047, 1.05 0.044, 0.082, 1.42
No. of reflections25922765
No. of parameters204204
No. of restraints04
H-atom treatmentOnly H-atom coordinates refinedH atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(Fo2) + (0.0137P)2 + 4.4877P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + 28.7093P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.68, 0.451.49, 2.50

Computer programs: COLLECT (Nonius, 1998), SMART (Bruker, 2001), EVALCCD (Duisenberg et al., 2003), SAINT (Bruker, 2001), EVALCCD, SAINT, SHELXTL (Sheldrick, 2001), DIAMOND (Brandenburg & Putz, 2004) and Mercury (Version 1.4; Bruno et al., 2002), SHELXTL and local programs.

Selected geometric parameters (Å, º) for (I) top
Cs—O13.352 (2)O4—C61.267 (3)
Cs—O2i3.2119 (19)O6—C81.253 (3)
Cs—O3ii3.1808 (19)O7—C41.439 (3)
Cs—O4iii3.1361 (19)C1—C41.542 (4)
Cs—O4ii3.469 (2)C3—C41.530 (4)
Cs—O5iv2.981 (2)C4—C51.502 (4)
Cs—O5v3.320 (2)C5—C61.395 (4)
Cs—O63.531 (2)C5—C81.399 (4)
Cs—O7vi3.040 (2)
C1—C4—C3113.3 (2)C6—C5—C8120.7 (2)
Symmetry codes: (i) x+1/2, y, z; (ii) x1/2, y+1, z; (iii) x1/2, y+1/2, z+1/2; (iv) x, y1/2, z+1/2; (v) x, y1, z; (vi) x1/2, y, z.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O7—H7···O40.93 (3)1.65 (3)2.563 (3)164 (3)
O8—H8···O60.72 (3)2.08 (3)2.780 (3)163 (4)
N1—H1N···O8v0.74 (3)2.16 (3)2.865 (3)161 (3)
N2—H2N···O3vii0.73 (3)2.09 (3)2.816 (3)174 (3)
N3—H3N···O1viii0.75 (3)2.57 (3)3.151 (3)136 (3)
N4—H4N···O7ii0.82 (3)2.29 (3)3.005 (3)147 (3)
Symmetry codes: (ii) x1/2, y+1, z; (v) x, y1, z; (vii) x+1, y+1, z; (viii) x, y+1/2, z+1/2.
Selected geometric parameters (Å, º) for (II) top
Cs—O2i2.983 (4)O4—C61.260 (6)
Cs—O3ii3.151 (4)O6—C81.269 (6)
Cs—O13.190 (4)O7—C41.421 (6)
Cs—O43.318 (4)C3—C41.534 (7)
Cs—O4iii3.009 (3)C4—C11.536 (7)
Cs—O5iv3.030 (3)C4—C51.531 (6)
Cs—O5v3.181 (4)C5—C61.403 (7)
Cs—O6ii3.690 (4)C5—C81.402 (6)
Cs—O7vi3.232 (4)
C3—C4—C1113.9 (4)C6—C5—C8120.0 (4)
Symmetry codes: (i) x+3/2, y1/2, z+3/2; (ii) x, y1, z; (iii) x+3/2, y1/2, z+2; (iv) x+1, y, z+2; (v) x+1/2, y1/2, z; (vi) x1/2, y1/2, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O7—H7···O40.85 (7)1.78 (7)2.567 (5)154 (6)
O8—H8···O60.79 (6)2.03 (6)2.817 (5)176 (6)
N2—H2N···O8vii0.86 (3)2.04 (3)2.864 (6)162 (6)
N1—H1N···O6i0.85 (3)2.16 (3)3.006 (5)176 (6)
N3—H3N···O3viii0.83 (3)2.52 (3)3.323 (6)164 (6)
N4—H4N···O1ix0.84 (3)2.18 (3)3.005 (6)168 (6)
Symmetry codes: (i) x+3/2, y1/2, z+3/2; (vii) x+1/2, y+1/2, z; (viii) x+3/2, y+1/2, z+2; (ix) x1/2, y+1/2, z.
 

Acknowledgements

The authors thank the EPSRC for funding.

References

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